摘要： Hydrogen storage in chemical compounds is a promising strategy to enable lightweight, high density, and safe hydrogen technologies. However, the hydrogen release rate from these chemicals is limited by the intrinsic catalytic activity of metal catalysts, which can be enhanced by using light irradiation. Here nanohybrids including a core of plasmonic TiN and multiple Pt nanocrystal catalytic centers are assembled and show, under resonant conditions at 700 nm, hot electrons driven hydrogen evolution from ammonia borane at an apparent quantum yield of 120%. It is also demonstrated that solar irradiation enhances the activity of TiN-Pt nanohybrids by one order of magnitude through two synergistic mechanisms: the hot electrons and collective-heating contributions. Using the microscopic calculation of the photoinduced temperature around a single nanocrystal, it is revealed that the collective plasmonic heating regime dominates the macroscopic temperature distribution in the system. The presented data show that plasmonic hot electrons and photothermal heating can be used in synergy to trigger hydrogen release from ammonia borane on demand, providing a general strategy for greatly enhancing the activity in the dark of metal catalysts.